Dyeing polyolefin articles with soluble dye and a short chain polyethylene glycol ether



United States Patent 3,385,652 DYEING PDLYULEFBN ARTICLES WITH SULUBLE DYE AND A SHURT CHAIN POLYETHYLENE GLYCOlL ETHER Andrew T. Walter, Charleston, and George M. Bryant and Robert G. Curtis, South Charleston, W. Va., assignors to Union Carbide Corporation, a corporation of New York No Drawing. Filed Aug. 21, 1963, Ser. No. 303,661 9 Claims. (Cl. 8-4) ABSTRACT OF THE DHSCLOSURE Applicants dye polyolefin articles, including mixtures of polyolefins and basic polymers with water soluble dyes and long chain alkyl and aryl ether of polyalkylene glycol with up to 8 --C H4O- units therein.

The present invention is concerned with an improved method of dyeing shaped polyolefin articles wherein one or more of the glycol derivatives hereinbelow defined are employed as dyeing assistants. The invention is also concerned with an improved dyebath composition for use in the dyeing of shaped polyolefin articles.

Unmodified polyolefins in the form of shaped articles, such as fibers and films, etc., have little inherent dyeability and heretofore have ordinarily not been satisfactorily dyed by conventional dyeing techniques which involve immersing the article to be dyed in a preferably heated aqueous dyebath containing the dyestufl and, generally, a dispersing agent. It is to be noted that the term dyeability as employed herein is intended to mean not only that an article be colored, but colored to a shade that is substantially resistant to the effects of light, Washing, dry cleaning, etc. In an attempt to improve the dyeability of polyolefins, minor amounts of various modifiers have been blended with the polymer. Such attempts have, in certain instances, met with limited success. The theory of carrier dyeing wherein a dyeing assistant, or carrier, is added to a dyebath in order to promote ultimate dye pick-up Without adverse elfect upon the properties of the dyed product is also known in the art. Unfortunately, the currently employed dyeing assistants are not, in general, purported to be significantly useful in connection with the dyeing of polyolefins.

In accordance with the present invention, a substantial improvement in the dyeability of shaped polyolefin articles by a wide variety of dyestuffs, including disperse dyestuffs, cationic dyestuffs, and acid and neutral dyeing premetallized dyestuffs, etc., is realized by the incorporation in an aqueous dyebath of a minor amount of at least one dyeing assistant of the formula:

wherein R is selected from the group consisting of the linear and branched-chain alkyl radicals preferably containing from 1 to about 8 carbon atoms and more preferably from 1 to 4 carbon atoms, the phenyl radical, and the R CO- acyl radicals wherein R is a linear or branched-chain alkyl radical preferably containing from 1 to about 4 carbon atoms; R is selected from the group consisting of hydrogen and the alkyl radicals of from 1 to 2 carbon atoms; R is selected from the group consisting of hydrogen and the linear and branched-chain alkyl radicals preferably containing from 1 to about 8 carbon atoms and more preferably from 1 to 4 carbon atoms; and x is a value of 1 to about 8 and preferably from 1 to ice 2. Thus, the dyeing assistants contemplated by this invention are known compounds and can be considered as monoether, diether, monoester, and ester-ether derivatives of monoor polyethylene glycols, monoor poly-1,2- propylene glycols, monoor poly-1,2-butylene glycols, poly(ethylene-1,2-propylene)glycols, etc. Mixtures of these glycol derivatives varying in molecular weight such that x, above, is an average value Within the aforementioned range are also contemplated as dyeing assistants; The particularly preferred dyeing assistants are the glycol derivatives having a limited solubility in water of from about 0.05 to about 5 grams/liter, and especially from about 0.2 to about 2 grams/liter, at 20 C., the eflectiveness of the dyeing assistant diminishing somewhat in certain instances as the solubility is varied outside this range.

By way of illustration, suitable dyeing assistants include:

ethylene glycol monoethyl ether, 1,2-propylene glycol monoethyl ether, ethylene glycol monobutyl ether, 1,2-propylene glycol monobutyl ether, ethylene glycol monohexyl ether, 1,2-propylene glycol monohexyl ether, ethylene glycol mono-Z-ethylhexyl ether, 1,2-propylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, 1,2-propylene glycol monophenyl ether, ethylene glycol diethyl diether, 1,2-propylene glycol diethyl diether, ethylene glycol dibutyl diether, 1,2-propylene glycol dibutyl diether, ethylene glycol methyl ethyl diether l,2propylene ethylene glycol methyl ethyl diether, ethylene glycol ethyl hexyl diether, 1 1,2-propylene glycol ethyl hexyl diether, diethylene glycol monoethyl ether, di-l,2-propylene glycol monoethyl ether, diethylene glycol monobutyl ether, dll,2-propylene glycol monobutyl ether, diethylene glycol monohexyl ether, di-1-,2-propylene glycol monoheXyl ether, diethylene glycol mono-Z-ethylhexyl ether, di-1,2-propylene glycol mono-Z-ethylhexyl ether, diethyleneglycol monophenyl ether, di-l,2-propylene glycol monophenyl ether, diethylene glycol diethyl diether, di-l,2-propylene glycol diethyl diether, diethylene glycol dibutyl diether, di-1,2-propylene glycol dibutyl diether, diethylene glycol methyl ethyl diether, dil,2-propylene glycol methyl ethyl diether, diethylene glycol ethyl hexyl diether, di-1,2-propylene glycol ethyl hexyl diether, triethylene glycol monoethyl ether, tri-l,2-propylene glycol monoethyl ether, triethylene glycol mono-Z-ethylhexyl ether, tri-l,2-propylene glycol mono-Z-ethylhexyl ether, triethylene glycol monophenyl ether, tri-1,2-propylene glycol monophenyl ether, triethylene glycol diethyl diether, tri-l,2-propylene glycol diethyl diether, triethylene glycol dibutyl diether, tri-1,2-propylene glycol dibutyl diether, triethylene glycol ethyl butyl diether, triethylene glycol ethyl phenyl diether, tri-l,2-propylene glycol ethyl butyl diether,

1 tetraethylene glycol monoethyl ether,

tetraethylene glycol mono-Z-ethylhexyl ether, tetraethylene glycol monophenyl ether, tetraethylene glycol diethyl diether, tetraethylene glycol dibutyl diether,

tetraethylene glycol ethyl butyl diether,

ethylene glycol monoacetate,

ethylene glycol monoacetate monoethyl ether, 1,2-propylene glycol monoacetate,

1,2-propylene glycol monoacetate monoethyl ether, ethylene glycol monobutyrate monoethyl ether, 1,2-propylene glycol monobutyrate monoethyl ether, ethylene glycol monoacetate monobutyl ether, 1,2-propylene glycol monoacetate monobutyl ether, ethylene glycol monobutryate monohexyl ether, 1,2-propylene glycol monobutyrate monohexyl ether, diethylene glycol monoacetate,

diethylene glycol monoacetate monoethyl ether, di-l,2-propylene glycol monoacetate monoethyl ether, diethylene glycol monobutyrate monoethyl ether, dil,2-propylene glycol monobutyrate monoethyl ether, diethylene glycol monoacetate monobutyl ether, di-1,2-propylene glycol monoacetate monobutyl ether, diethylene glycol monobutyrate monohexyl ether, di-1,2-propylene glycol monobutyrate monohexyl ether, triethylene glycol monoacetate,

triethylene glycol monoacetate monoethyl ether, tri-1,2-propylene glycol monoacetate,

tri-1,2-propylene glycol monoacetate monoethyl ether, triethylene glycol monobutyrate monoethyl ether, tri-l,2-propylene glycol monobutyrate monoethyl ether, triethylene glycol monoacetate monobutyl ether, tri-1,2-propylene glycol monoacetate monobutyl ether, triethylene glycol monobutyrate monohexyl ether, tril,2-propylene glycol monobutyrate monohexyl ether, tetraethylene glycol monoacetate,

tetraethylene glycol monoacet'ate monoethyl ether, tetraethylene glycol monobutyrate monobutyl ether, tetraethylene glycol monoacetate monobutyl ether, tetraethylene glycol monobutyrate monohexyl ether,

and the like. Other suitable dyeing assistants include the mixture of glycol derivatives produced by the conventional reaction of an alkanol or phenol with ethylene oxide, 1,2-propylene oxide or a mixture thereof in a proportion such that there is an average of up to about 8 alkylene oxide units per molecule in the resulting product. The effectiveness of a given dyeing assistant may vary somewhat depending upon the particular dyestuff employed. Thus, the optimum dyeing assistant can readily be determined by one skilled in the art in light of this disclosure.

The polyolefins contemplated by this invention include the known, normally solid polyolefins produced by the conventional homoor copolymerization of one or more mono-alpha-olefins containing from 2 to about 12 carbon atoms, such as ethylene, propylene, 4-methylbutene-1, 4-methylpentene-l, hexene-l, dodecene-l, allylcyclohexane, etc. The preferred polyolefins are .the polypropylenes having a density above about 0.89 grams/cubic centimeter and a melt indeX of below about 100 decigrams at 230 C. The shaped polyolefin articles for which improved dyeability is realized in accordance with this invention, such as fibers, films or the like, can be produced from these polyolefins by conventional spinning, extrusion, molding or milling operations, etc.

It is also known that dyeability of polyolefins is enhanced to some extent by blending with preferably minor amounts of various modifiers, particularly normally solid polymeric modifiers such as the copolymers produced by the conventional polymerization of ethylene with from about 0.5 to about 50 percent by total weight of a copolymerizable monomer, as typical of which there can be mentioned (a) the N-saturated aliphatic and aromatic hydrocarbyl N vinylacetamides preferabiy containing from 1 to about 12 carbon atoms in the N-hydrocarbyl moiety thereof, such as N-methyl-N-vinylacetamide, N- cyclohexyl-N-vinylacetamide, N 2 ethylhexyl-N-vinylacetamide, N phenyl N vinylacetamide, N benzyl-N- 4 vinylacetamide, N-tolyl-N-vinylacetamide, etc. (b) the N- vinylheterocycles of the formula:

III COOR COOR wherein M is an alkali metal atom, 11 is a value of from 2 to about 5, and R is an alkyl radical as hereinabove defined in connection with Formula I, such as dirnethyl 4-(4- sodium-sulfophenoxyethoxy)isophthalate, di-2-ethylhexyl 5 (4 sodiumsulfophenoxyethoxy)phthalatc, dimethyl 4- (4 potassiumsulfophenoxypentoxy)terephthalate, etc. Shaped polyolefin articles produced from such blends are also within the contemplation of this invention, a further improvement in the dyeability of such shaped polyolefin articles being realized through the practice of this invention. In this regard, particularly useful modifiers in connection with disperse and premetallized dyeability are the copolymers of ethylene and N-alkyl-N-vinylacetamides preferably containing from about 60 to about 95 percent by weight of polymerized ethylene, such copolymers being preferably present in the blend in a proportion of from about 1 to about 20 percent by total weight. Similarly, cationic dyeability is particularly well enhanced using a like proportion of an alkyl ester of an alkalimetalsulfophenoxyalkoxyisophthalic acid. Other conventional additives, such as heat and light stabilizers, organometallic chelating agents, etc., can also be incorporated in the polyolefin articles.

Suitable dyestuffs which can be employed in accordance with this invention include the premetallized dyestuffs such as:

Vialon Fast Yellow G C.I. Acid Yellow 118 Vialon Fast Yellow R C.I. Acid Yellow 119 Cibalan Yellow FGL C.I. Acid Yellow 128 Cibalan Red ZGL C.I. Acid Red 211 Lanasyn Red BL C.I. Acid Red 215 Vialon Fast Red B C.I. Acid Red 225 Cibalan Blue BL C.I. Acid Blue 168 Vialon Fast Blue-Grey B C.I. Acid Black 61 the disperse dyestuffs such as: Latyl Blue FLW C.I. Disperse Blue 27 C.I. 60767 Celliton Fast Red GGA C.I. Disperse Red 17 C.I. 11210 Calcosyn Yellow GC Cone. s C.I. Disperse Yellow 3 Artisil/Foron Brilliant Pink FG C.I. Disperse Red 55 the cationic dyestuffs such as:

Sevron Blue 5G C.I. Basic Blue 4 C.I. 51004 and C.I. 48055 Sevron Brilliant Red 4G C.I. Basic Red 14 C.I. Basic Yellow 11 C.I. 51004 and Sevron Yellow R C.I. 48005 and the like. Any other dyestufi to which the shaped polyolefin article is receptive can also be employed as described herein.

In the practice of this invention, one or more of the dyeing assistants hereinabove described are incorporated in an aqueous dyebath additionally comprising water, the dyestufr, and preferably a dispersing agent, particularly an anionic or nonionic dispersing agent, such as sodium N-methyl-N-oleoyltaurate, isobutyldodecyl sodiumsulfate, polyethylene glycol nonyl phenyl diether, etc. Typically, the dyebath is comprised of water, from about 0.1 to about percent by weight of the dyestuif, from about 0.1 to about 20 percent by Weight of the dispersing agent, and from about 0.1 to about 35 percent by weight of the dyeing assistant, such percentages being based upon the weight of the shaped polyolefin article to be dyed. The operable proportions of each of these components however, are not narrowly critical, and can be varied more broadly as determined by one skilled in the art in light of this disclosure. Preferably the dyebath is comprised of water, from about 1 to about 3 percent by weight of the dyestutf, from about 0.5 to about percent by weight of the dispersing agent, and from about 1 to about 20 percent by Weight of the dyeing assistant, based in like manner. The amount of water employed to make up the dyebath can also vary broadly and is dependent upon the total dyebath to polyolefin ratio desired, such ratio preferably being in the range of 10:1 to 50:1. Other bath additives can also be incorporated. For instance, a small amount of a suitable basic compound, such as ammonium acetate, diamrnonium sulfate, diammonium phosphate, etc., can be employed in this regard in order to bring and/ or maintain the pH of the dyebath on the neutral or alkaline side, particularly in connection with premetallized dyeings.

In making up the dyebath, the dyeing assistant is preferably initially admixed with a dispersing agent in a small amount of warm water. The dispersed dyeing assistant is then added to an aqueous solution of the dyestulf, followed by the introduction of any other bath additives. Upon bringing the dyebath up to the desired bath to polyolefin ratio, the shaped polyolefin article is immersed in the dyebath and heated preferably at a temperature of from about 80 C. to 100 C., or at the boil, for the desired period of time as determined, for instance, by the degree of coloration desired. Higher temperatures accompanied by superatmospheric pressures can also be employed. The dyed article is then removed from the dyebath, rinsed, scoured, rinsed again and dried. This procedure can also be varied in any other convenient manner.

It is to be pointed out that, through the practice of this invention, a number of advantages can be realized as compared with similar operations in which the dyeing assistant of this invention is omitted. Firstly, the dyeability of the shaped polyolefin article, as measured in terms of dye pick-up, is substantially enhanced. The premetallized dyeings are particularly outstanding because of the deep shades and excellent fastness obtained. In addition, the invention provides a convenient means for coloring shaped polyolefin articles with the class of disperse dyes which have heretofore not been found completely satisfactory in the dyeing of such articles. Moreover, the physical properties of the shaped polyolefin articles dyed in accordance with this invention are not: detrimentally affected due to the presence of residual dyeing assistant, and the dyeings are acceptably fast and light stable.

The practice of this invention and the advantages accruable in accordance therewith can be illustrated further by the following specific examples. In the examples, percentages are based upon the Weight of fibers being dyed. The amount of dye on the fiber, or the depth of color obtainedis approximately directly proportional to the K/S value, which is a measure of the light reflected from the sample, K/S being equal to (1r) /2r, wherein r is the reflectance at the maximum absorption wave length. The determination and significance of K/S values are described more fully in the article by D. -B. Judd, Color in Business, Science and Industry, 1952, pp. 314-342.

Example I (a) Five grams of staple fibers spun from a blend of about parts by weight of polypropylene and about 10 parts by weight of a copolymer of about 80 par-ts by weight of ethylene with about 20 parts by weight of N- methyl-N-vinylacetamide were added at room temperature to 250 ml. of an aqueous dyebath containing 1 percent by weight of sodium N-methyl-N-oleoyltaurate, 20 percent by weight of diethylene glycol monohexyl ether and 3 percent by weight of Latyl Blue FLW. The temperature of the dyebath was raised to the boil C.- C.) and maintained for 90 min. The fibers, now dyed to a deep shade, were removed from the dyebath, rinsed with water, scoured at 80 C. for 30 min. with an aqueous solution containing 1 percent by weight of a polyethylene glycol nonyl phenyl diether and 0.5 percent by Weight of soda ash, rinsed again, and finally air-dried. A control was also conducted omitting the use of the dyeing assistant, whereupon the fibers were dyed to a substantially lighter shade of blue. The extent of dyeing obtained was also measured colorimetrically in terms of K/S values K/S With dyeing assistant 10.4 Control a- 5.2

K/S With dyeing assistant 19.4 Control 11.4

Example II *(a) In a manner similar to that described in Example I, a series of experiments were conducted in each of which 5 g. of the polyolefin fibers described in Example I were dyed using a dyebath in which an equal weight of various glycol derivatives were substituted as the dyeing assistant and an equal weight of Cibalan Red 2GL was substituted as the dyestufi. A control was also conducted omitting the use of the dyeing assistant, the fibers being dyed thereby to a substantially lighter shade.

Dyeing assistant: K/ S Diethylene glycol dibutyl diether 16.6 Diethylene glycol mono-Z-ethylhexyl ether 15.9 Diethylene glycol ethyl hexyl diether 13.9 PGMB 1 13.3 Ethylene glycol dibutyl diether 12.4 Tetraethylene glycol dibutyl diether 11.5 Diethylene glycol monohexyl ether 9.4 Ethylene glycol monohexyl ether 7.4

Diethylene glycol mono-acetate monobutyl ether 5.8 Ethylene glycol mono-acetate monobutyl ether 5.8 Control 4.1

A polypropylene glycol monobutyl ether containing an average of about 6 oxypropylene groups per molecule.

(b) In another series of experiments conducted in a manner similar to that described above in this example, various glycol derivatives were substituted as the dyeing assistant in varying amounts, viz 5, 10, and 15 percent by weight.

Dyeing assistant Cone,

percent Dietgylene glycol hexyl ether diethcr Do Tetrgethylene glycol dibutyl diether A polypropylene glycol monobutyl ether containing an average of about (i oxyprupylene groups per molecule.

Example III Five grams of staple fibers spun from unmodified polypropylene were dyed using the dyebath described above in Example 1(1)). The dyebath containing the fibers was placed in a pressure cooker. The pressure cooker was sealed and heated to 120 C. over 30 min. The temperature was maintained at this level for an additional 60 min. The pressure was then released and the dyed fibers were removed from the dyebath, rinsed, scoured, rinsed, and dried as described above in Example 1(a). A control was also conducted omitting the use of the dyeing assistant, the fibers being dyed thereby to a substantially lighter shade.

K/ S With dyeing assistant 1.03 Control 055 Example IV Five grains of tubing knit from filament yarn spun from a blend of about 90 parts by weight of polypropylene and about parts by weight of a copolymer of about 80 parts by weight of ethylene with about parts by Weight of N-vinyl-Z-pyrrolidone were dyed in a manner similar to that described in Example I using a dyebath in which an equal weight of ethylene glycol dibutyl diether was substituted as the dyeing assistant and an equal weight of Celliton Fast Red GGA was substituted as the dyestuif. A control was also conducted omitting the use of the dyeing assistant, the fibers being dyed thereby to a substantially lighter shade.

K/ S With dyeing assistant 12.9 Control 11.2

In similar manner, the dyeability of the yarn is improved using a dyebath in which an equal weight of a 50:50 poly(ethylene-1,2-propylene) glycol monobutyl ether containing an average of about 4 oxyalkylene groups per molecule is substituted as the dyeing assistant.

Example V (a) A 5 g. skein of fibers spun from a blend of about 90 parts by weight of poly(4-methyl-2-pentene) and about 10 parts by weight of a copolymer of about 75 parts by weight with about parts by weight of N-methyl-N- vinylacetamide was dyed to a deep shade in a manner and using a dyebath similar to that described in Example 1(1)). A control was also conducted omitting the use of the dyeing assistant, the fibers being dyed thereby to a substantially lighter shade.

(b) A similar series of experiments was conducted in which an equal amount of unmodified polyethylene was substituted for poly(4-methyl-l-pentene) in producing the polyolefin fibers of this example. Here again, the fibers were dyed to a deep shade using the dyeing assistant of this invention and to a substantially lighter shade by the control.

Example VI (a) Five grams of fibers spun from a blend of about parts by weight of polypropylene and about 5 parts by weight of the di-2-ethylhexyl diester of 5-(4-sodiumsulfophenoxyethoxy) isophthalic acid was dyed to a deep shade in a manner and using a dyebath similar to that described in Example 1(1)). A control was also conducted omitting the use of the dyeing assistant, the fibers being dyed thereby to a substantially lighter shade.

(b) A similar series of experiments were conducted in which an equal weight of Sevron Blue 56 (pasted with acetic acid) was substituted as the dystuif and an equal weight of a polyethylene glycol nonyl phenyl diether was employed as the dispersing agent. Here again, the fibcrs were dyed to a deep shade using the dyeing assistant of this invention and to a substantially lighter shade by the control.

What is claimed is:

1. The method of dyeing a shaped polyolefin article with a water-soluble dyestuif to which said polyolefin artiole is receptive, comprising heating said shaped polyolefin article in an aqueous dyebath containing said dyestutf and a dyeability-improving amount of a glycol derivative of wherein R is selected from the group consisting of the alkyl radicals of from 1 to 8 carbon atoms, the phenyl radical, and the R CO acyl radicals wherein R is an alkyl radical of from 1 to 8 carbon atoms, R is selected from the group consisting of hydrogen and the alkyl radicals of from 1 to 2 carbon atoms, R is selected from the group consisting of hydrogen and the alkyl radicals of from 1 to 8 carbon atoms, and x is a value of from 1 to about 8.

2. The method of dyeing a shaped polyolefin article with a water-soluble dyestutf to which said polyolefin article is receptive, comprising heating said shaped polyolefin article in an aqueous dyebath containing said dyestuif and a dyeability-improving amount of a glycol derivative of the formula:

wherein R is selected from the group consisting of the alkyl radicals of from 1 to 8 carbon atoms, the phenyl radical, and the R CO acyl radicals wherein R is an alkyl radical of from 1 to 8 carbon atoms, R is selected from the group consisting of hydrogen and the alkyl radicals of from 1 to 2 carbon atoms, R is selected from the group consisting of hydrogen and the alkyl radicals of from 1 to 8 carbon atoms, and x is a value of from 1 to about 8, said glycol derivative having a solubility in water, at a temperature of 20 C., of from about 0.05 to about 5 grams/liter.

3. The method in accordance with claim 2 wherein said glycol derivative is ethylene glycol dibutyl diether.

4. The method in accordance with claim 2 wherein said glycol derivative is ethylene glycol monohexyl ether.

5. The method in accordance with claim 2 wherein said glycol derivative is diethylene glycol dibutyl diether.

6. The method in accordance with claim 2 wherein said glycol derivative is diethylene glycol mono-2-ethylhexyl ether.

7. The method in accordance with claim 2 wherein said glycol derivative is tetraethylene glycol dibutyl diether.

8. The method in accordance with claim 2 wherein said glycol derivative is polypropylene glycol monobutyl ether containing an average of about 6 oxypropylene groups per molecule.

9. The method of dyeing a shaped polyolefin article with a water-soluble dyestuif to which said polyolefin article is receptive, comprising heating said shaped polyolefin article in an aqueous dyebath containing said dyestulf and a glycol derivative of the formula:

| E (CHCHaOMR:

wherein R is selected from the group consisting of the alkyl radicals of from 1 to 8 carbon atoms, the phenyl radical, and the R CO- acyl radicals wherein R is an alkyl radical of from 1 to 8 carbon atoms, R is selected from the group consisting of hydrogen and the alkyl radicals of from 1 to 2 carbon atoms, R is selected from the group consisting of hydrogen and the alkyl radicals of from 1 to 8 carbon atoms, and x is a value of from 1 to about 8, said glycol derivative being incorporated in said dyebath in a proportion of from about 1 to about percent by weight based upon the weight of said polyolefin article.

References Cited UNITED STATES PATENTS 2,828,180 3/ 1959 Sertorio 855 2,983,651 5/1961 Seemuller 8-93 X 3,069,220 12/1962 Dawson et al. .a 893 X 3,206,420 9/1965 Smart et al 893 X NORMAN G. TORCHIN, Primary Examiner. 

